Metal tarnish remover



Patented Jan. 29, 1946 UNITED STATES PATENT OFFICE METAL TARNISH REMOVERNo Drawing. Application January 19, 1943, Serial No. 472,903

13 Claims.

This invention relates to a tarnish remover and the object of theinvention is to provide an improved composition in this class ofmaterials.

As usually made, metal polishes comprise an abrasive material togetherwith a carrier such as petrolatum, hydrocarbon oils, glycerine or water,with or without soap or an emulsifying agent. The use of carriers ofthese types of materials is disadvantageous in certain respects. Thepetrolatum, hydrocarbon oils, glycerine and water are substantiallyinert with respect to the tarnishes, for instance metallic oxides orsulphides which are to be removed from the metal. Moreover, an oil orgrease cannot be washed from the polished article unless a specialsolvent or emulsifying agent is used as the grease or oil is insolublein water. Additional difficulties with water-soluble soaps and similarmaterials are that they tend to react with a number of abrasivematerials, for instance iron salts or calcium salts, to formwater-insoluble soaps which decrease the efiiciency of the abrasivecompositions and are difficult to remove from the cleaned metal. Thetarnish removers of the present invention should not be confused withthe usual so-called polishes, for instance shoe polishes or floorpolishes, as the action of the compositions of the present invention isto remove tarnish films from the metal while the action of a shoe polishor floor polish is merely to provide a masking covering or a lustrousfilm.

A tarnish, as the term is used in the present description, is intendedto define that film discoloration of the metal surface which occurs by achange in the metal, for instance by the formation of a sulfide or oxidefilm which is apparently integral with the metal surface and may belikened to a metal corrosion; it is distinct from the mere surface layerof dust or dirt or other foreign matter which may deposit on a metalsurface and dull it. While the tarnish removers of the present inventionwill remove surface dirt, their action is more than a mere detergentaction and is different from a mere scouring or abrasive or buffingaction. A detergent action is exemplified by the action of soap andwater, the surface dirt merely being washed away. In a scouring orbuffing action, undesirable surface adhesions are merely cut away fromthe surface by the abrading or grinding or cutting action of thescouring or abrasive material. With the compositions of the presentinvention, there appears to be a breaking down or change in either orboth of the physical and chemical structure of the tarnish whereby thetarnish is removed with a minimum of mechanical effort. The action ofthe essential ingredient, a polyoxyethylene diol, is not wholly chemicalas it may be permitted to remain in contact with the tarnish withoutremoving the tarnish and Without apparent change in the tarnish; but theaction is more than a mere abradant action as a solution of thepolyoxyethylene diol in water removes tarnish better than a mixture ofonly abradant and water, and the action is apparently not a combinationof detergent and abradant action nor a mere detergent action as asolution of the said diol in water removes tarnish better than a mixtureof soap and water while a composition of the said diol, abrasive andwater removes tarnish better than a composition of soap, abrasive andwater. The pglyoxyethylene diols appear to act on the tarnishiii'an'ianner which enables the tarnish to be removed mechanically, as asolution of 15% of the polyoxyethylene diol in of water is effectivewhen forcefully rubbed on the tarnish although the most pronouncedeffect is obtained when an abradant is included. Furthermore, water mustbe present when the composition is used to remove tarnish and thepolyoxyethylene diol must be present as a free substance in an amountnot less than about 15% by weight of the total composition. When appliedto the tarnish, for effective removal thereof, the polyoxyethylene diolmust be in solution in water so that the diol molecule is carried intoand can attack the tarnish, for example if a buffing cake composed of asolid polyoxyethylene diol and an abrasive is rubbed against a tarnishedmetal surface, the action appears to be purely an abrasive action, thepolyoxyethylene diol acting merely as a carrier for the abrasive; but ifa composition containing the polyoxyethylene diol, abrasive and water isused so that the said diol is in a condition of molecular distributionin the solvent and can attack the tarnish, the tarnish is easily removedwith a minimum of mechanical effort and abrasive action and hence with aminimum of scratching the metal surface.

The tarnish removing composition of my invention comprises as anessential ingredient at least about 15% by weight of a polyoxyethylenediol of the 1,2 series, preferably 'bne containing sulficient chemicallycombined oxyethylene radicals to be normally solid, and a solvent forthe diol. The tarnish remover preferably also contains an abrasive andmay contain other and additional ingredients, which may conveniently bereferred to as addends, to assist in removing the tarnish which formsthe undesirable discol- 2 asoaaee oration on the metal surface. Thebasic ingredients of the tarnish remover, i. e. the polyoxyethylene dioland its solvent. are, in combination, an efiective tarnish remover yetthey are not greasy, they do not form water-insoluble films norprecipitates and, after the tarnish is removed, the compound may easilybe removed from the metal merely by flushing with water. Thus, theentire operation of removing the tarnish and the iinal cleansing of thetreated article is reduced to a very eflicient but simple operation.

These and other objects and features of the invention will more fullyappear as obvious or will be pointed out in the following descriptionand accompanying claims.

The polyoxyethylene diols may be formed by the reaction of ethyleneoxide with ethylene glycol in the presence of an alkaline catalyst, andwith the degree of the addition of the ethylene oxide controlledtoproduce the molecular size desired. For instance, ethylene oxide may bereacted with ethylene glycol or other alkyiene glycols ,oflow molecularweight and of the 1,2- series to give the polyoxyethylenediols. when thepolyoxyethylene diols are referred to as having given molecular weightsor average molecular weights, it is understood that the mass may be amixture of polyoxyethylene diols of different molecular weights. Forinstance, ethylene glycol has a molecular weight, in round numbers, of62 and each ethylene oxide radical has a molecular weight of 44.Polyoxyethylene diol composed of 19 ethylene oxide radicals added to oneethylene glycol molecule has a molecular weight of 898. Apolyoxyethylene diol having an average molecular weight of 900 may thusbe a mixture of polyoxyethylene diols wherein, for instance, there maybe some polyoxyethylene diol molecules containing 18 or less, and somecontaining 20 or more ethylene oxide radicals, but the molecular weightor the average molecular weight of the mass as determined by test isabout 900. Polyoxyethylene diols having an average molecular weight ofabout 900 are normally solid, having a fusion or melting point of about30 C. to 40 C. Polyoxyethylene diols having an average molecular weightof about 400 are fluids. For the purposes of this invention, I prefer touse a polyoxyethylene diol composition of the type disclosed herein,containing sufl'ic'ient oxyethylene radicals to form a normally solidpolyoxyethylene diol, such preferred polyoxyethylene diol compositionhaving an average molecular weight of approximately 900. For the purposeof this disclosure, the term polyoxyethylene diol" i s intended toinclude the polyoxyethylene diol composition indicated, and the termsolid" is intended to refer to materials which are semi-solid and willhold their shape at normal temperatures of approximately 20 C. asdistinguished from those which are distinctly liquids and incapable ofholding a given shape at normal temperatures.

The polyoxyethylene diols previously described are sufiiciently solublefor the purposes of this invention, in many different solvents, forinand soft water and thus there is always ready at hand a low costsolvent. Furthermore, the water and polyoxyethylene diols appear to havea cooperative action, particularly with an abrasive and addendshereinafter described, in removing tarnish from metals.

The polyoxyethylene diols having the higher average molecular weightsare harder than those of the lower average molecular weights and havehigher melting points. A polyoxyethylene diol having an averagemolecular weight of approximately 900 (as determined by the Menzies andWright method of determining molecular weights, described at page 2314,volume 43 (1921) of the Journal of the American Chemical Society) has adensity of approximately 1.151 grams per 0. c. at C., a melting point ofapproximately C. to 0., a viscosity of approximately to 90 SayboltUniversal seconds at 210 F., and a flash 20 point of approximately 430F. A polyoxyethylene diol having an average molecular weight ofapproximately 3,500 (determined by the same method) has a density ofapproximately 1.204, a melting point of approximately 54 C. to 57 0., aviscosity of approximately 400 to 600, and a flash point ofapproximately 535 F. A polyoxyethylene diol having an average molecularweight of approximately 6,000 has a melting point of about 60-65 C. Theliquid polyoxyethylene diols have average molecular weights beginning inthe neighborhood of 200 and running up to about 500 when they begin toassume the consistency of the 900 molecular weight material previouslydescribed. In preparing the compositions contemplated herein, I may usethe polyoxyethyl. ene diols which are liquids and those which havemolecular weights substantially higher, say a molecular weight ofapproximately 2,500, but prefer those which have a molecular weight ofapproximately 900, these being soit solids. Polyoxyethylene diols havingmolecular weights of approximately 900 appear to be more efiective, whenused with water and an abrasive as a tarnish remover,

than the fluid polyoxyethylene diols and those which have molecularweights of approximately 4,000. Tarnish may be removed merely byapplying to the tarnish, by means of a wet applicator, for instance acloth, onge or brush. a normally solid polyoxyethylene diol having amelting point between about 30 C. and 40 C. and then forcefully rubbingthe tarnish. This particular diol is of a petrolatum-like consistencyand readily soluble in water and is so effective in removing tarnish,that whether it be applied directly to the tarnish and then rubbed witha wet applicator or the wet applicator first be rubbed on the diol,

suilicient of the diol is normally applied to give at least the 15%minimum concentration (with "the water of the applicator) to provide aneifective tarnish remover. If desired, the diol may have abrasive mixedwith it.

stance both hard and soft water aswell as aro- All of thesepolyoxyethylene diols may be prepared free from odor and have theproperty of forming clear, colorless and stable solutions, with eitherhard or soft water. Those which are solids may be used to formcompositions having the consistency of thick or thin creams, by theaddition of suitable amounts of water or liquid polyoxyethylene diol orother liquid ingredient. Thepolyoxyethylene diols which have an averagemolecular weight of approximately 900 are slightly hygroscopic and takeon a moist appearance under humid conditions. The range of averagemolecular weights of the polyoxyethylene diols for the most eflectlvepolishes is from approximately 700 to 2,500. These polyoxyethylene diolsare almost immediately dissolved in water when rubbed therewith betweenthe fingers and those having higher average molecular weights aredissolved somewhat like hard soaps. However, the polyoxyethylene diolsare soluble in hard and soft, hot and cold water, the solutions areclear as distinguished from the colloidal solutions which have theopalescent effect produced by soaps, and they do not form a precipitateor curd in hard water. Thus, the polyoxyethylene diols remain insolution and remain effective as an ingredient of the tarnish removerwhereas oils and soaps may not.

The polyoxyethylene diols are usually considered to be quite inertwith-respect to metals and to the materials usually used in metalpolishes. In mere admixture with water, abrasive materials such aschalk, diatomaceous earth, metal salts, silica, rouge and the like, orother ingredients such as acids, for instance oxalic acid, citric acid,tartaric acid and the like, alkalis, for instance sodium hyposulfite,potassium tartrate or bitartrate, alkyl or alkylol amines, for instanceethanol amines or reaction products of these materials, forinstancetriethanol amine acid oxalate, and monoethanolamine acid tartrate, thepolyoxyethylene diols appear to be inert with respect to the otheringredients when combined in the proportions used in my tarnish removersand at ordinary room or atmospheric temperatures.

However, when applied to oxidized, sulphurized or otherwise tarnishedmetal and rubbed on the tarnished area in conjunction with water, withor without an abrasive, the polyoxyethylene diols have an action whichremoves the tarnish. Thus, in a composition comprising a normally solidpolyoxyethylene diol, chalk and water, ther appeared to be no reactionbetween the ingredients (except that the water dissolved thepolyethylene glycol) at room temperature yet, when the composition wasforcefully rubbed on tarnisn on steel dies, the tarnish was removedbetter than with metal polishes currently on the market. A compositioncomprising the normally solid polyoxyethylene diol, chalk and water,also was more effective than would be expected from comparative testseither with a mixture of the said diol and chalk, or chalk and water. Amix comprising only the normally solid polyoxyethylene recognized. Forinstance, if the abrasive is chalk (calcium carbonate) or rouge (ironoxide), the probability of a chemical reaction must be recognized if anacid is used as an addend. But if it be desired to formulate a tarnishremover which is particularly effective on a certain metal or alloy, fgrinstance copper or brass, and an acid, for Instance dilute hydrochloricacid, is a desirable addend, the abrasive may be powdered silica orother material which is substantially unafl'ected by the acid.

Addends of general utility are materials such as wetting agents andpenetrating agents. The

polyoxyethylene diols have the action of spreading and levelling agentsand they appear to work particularly effectivel in tarnish removers withthe addition of a small amount of a wetting agent or a penetratingagent. Wetting or penetrating agents which have emulsifyingcharacteristics may, of course, be incorporated but such use of theseagents is due primarily to other characteristics which they may possesand not to their emulsifying characteristics. In a broad aspect of theinvention, a wetting or penetrating agent of general wetting orpenetrating characteristics may be used but a particularly effectiveclass of wetting and penetrating agents are those containing organicradicals and combined sulfur and, in particular, the wetting agents nextdescribed which have been found to give exceptional results with thepolyoxyethylene diols when used for removing v tarnish. These agentsare, in general, basically diol and water appeared to be more efficientthan glycerine or a mix comprising only glycerine and water.

The molecular size of the polyoxyethylene dicl appears to have arelation to the efficiency of the compositionin its action in removingtarnish as in comparing the effect of compositions which were identicalin weights of ingredients, and differed only in that polyoxyethylenediols having average molecular weights of 400, 900 and 3,500 were usedin the respective compositions. the composition containing the 900molecula weight polyoxyethylene diol appeared to be more efficient thanthe other two.

Withthe basic formula of polyoxyethylene die.

and water mains used other; materials (in addi tion to the abrasive) ofgeneral are: specific utility and a feature of the invention is a basicformula of neutral ingredients with which substantially any addedmaterial orfaddend" may he u sed. The preferred addends are chemicallyor physically active either on the tarnish or as wetting or penetratingagents. Of course. the possible chemical reactions between the abrasiveand the addend or between the addends must be esters carrying combinedsulfur in the form of a sulfite, sulfate, or sulfonate group. The saidsubstances may be alkyl or aryl metal sulfates, the metal preferablybeing an alkali or an alkali earth metal. The substances also may beclassed as salts of oxysulfur organic compounds. They include the saltsof the sulfated high molecular weight alcohols, sulfonated esters ofdibasic acids and higher alcohols, and alkylated aryl sulfonates. Saltsof the sulfate ester derivatives of the higher saturated, branched-chainaliphatic alcohols including both the primary and secondary alcohols,are suitable. These sulfate esters may be those of the alkali metalhydroxides, the ethanol amines and of other bases. Sulfate esterderivatives of the higher saturated branched-chain aliphatic alcoholswhich are described in the United States patent to Wickert No.2,088,019, dated July 27, 1937, are satisfactory for my purposes.

Other salts of oxysulfur organic compounds which may be used includesalts of various sulfonated higher fatty alcohols obtained from fats andoils of animal and vegetable origin, salts of the alkylated arylsulfonates, and the salts of the diaryl esters of sulfosuccinic acid,such as for example, the dioctyl ester and the dihexyl ester of sodiumsulfosuccinie acid. Surface active wetting agents of the type of fattyalcohol sulfates are also contemplated. In general, good results may beobtained with these previously described surface active wetting agentshaving from 8 to 20 carbon atoms per molecule. Salts of the sulfateester derivatives of the saturated branched-chain aliphatic alcohols arepreferred, however, and especially good results were obtained from thosehaving from 8 to 17 carbon atoms to the molecule.

These substances are all miscible with water in sufficient amount to actas extremely effective surface-wetting agents when used in conjunctionwith the said diols, even though minute quantities are incorporated.

addends of specific utility are those which areparticularly"eiilaclbusfor the tarnish on any speciiic metal. Forinstance; chloride of lime, bicarbonate of soda or magnesia, sodiumchloride or dilute acids, for instance, inorganic acids such ahydrochloric acid or sulfuric acid or organic acids, such as acetic acidor oxalic acid, may be used in conjunction with the polyoxyethylenediols for removing the tarnish from gold. In the case of tarnished brassand co the tarnish removers may contain addends such as oxalic acid,hydrochloric acid, sulfuric acid,=, chromic acid, nitric acid, tartaricacid, citric acid, cream of tartar, alum, sodium chloride, and ammoniumchloride.

Silver-tarnish removers may contain such addends as borax, ammoniumcarbonate, paris white,fj so dium or potassium hyposuliit; sodiumchloride, potassium cyanide, nitric acid. calcium chloride, sodium orpotassium hypochlorite, alum, potassium or sodium nitrate, camphor,ammonia, potassium or sodium sulfate, oxalic acid, subcarbonate of iron,silver nitrate, sodium or potassium carbonate, citric acid and the like.

Tarnish removers for iron and steel and other (base metals may containsubstantially any of the addends previously listed, for instance bluevitriol,

borax, prussiate of potash, arsenous acid, antimony trichloride, sodiumcarbonate, sulfuric acid, nitric acid, oxalic acid and the like.

. Substantially any abrasive may be used in the tarnish remover, forinstance charcoal, chalk, rouge, tripoli, pumice, brick, pipe clay,yellow ocher, emery, rotten stone, silica, sand, flint. infusorialearth,red lead, white lead, and the like. These abrasives are water insoluble.

Although substantially any amount or kind of abrasive may be used'in thetarnish remover, abrasives such as chalk and the like may also serve asthickening agents to produce a thickor thin cream type product asdesired. The presence of the polyoxyethylene diols renders the tarnishremover so efllcacious that only relatively small amountsof the addendsneed be used. This is desirable as the usual addends are frequently hardon the skin but theopposite is true of the polyoxyethylene diols. Also.due to the eiilcacy of a tarnish remover containing a polyoxyethylenediol and the fact that the necessity for mechanical effort and abrasiveaction is reduced over that required for a product which contains noneof the said diol, a soft abrasive, for instance chalk or rouge, or anabrasive of smaller particle size can be used if the tarnish removercontains a polyoxyethylene diol, in cases where a hard, coarser abrasivesuch as emery or silica has heretofore been required. The soft or fineabrasive does less harm and leaves less scratches on the metal than doesa hard, coarse, sharp abrasive.

In further explanationof the invention, reference may be had to thefollowing formulae which, it should be understood, are given merely byway of example and without intent to limit the invention totheingredients or the proportions thereof which are specificallydisclosed.

Example 1 Twenty parts of water, 38 parts of polyoxysulfate esterderivative of 3,9-diethyltridecanol- 6). It is a stable, water-solubleliquid. Other wetting agents containing sulfur in chemical combinationmay be used instead of the one given. For instance, any of the followingmay be used; sodium octyl sulfate (monosodium sulfate ester derivativeof 2-ethyl hexanol-l); sodium tetradecyl sulfate (sodium sulfate esterderivative of 'l-ethyl, 2 methyl undecanol-S); dioctyl ester of sodiumsulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; a fattyalcohol sulfate; sodium tetradecyl sulfate (sodium sulfate esterderivative of 'l-ethyl, 2 methyl undecanoli). Into these ingredients areincorporated 39 parts of finely ground chalk orwhite rouge. The mixtureforms a still cream type product which may be made thicker or more fluidby adjusting the amount of the said polyoxyethylene diol or the abrasiveor the water. A thinner product may also be made by substituting a fluidpolyoxyethylene diol for all or a portion of the solid polyoxyethylenediol which has an average molecular weight of 900, referred to in thefirst part of this example. Also, a thicker product may be made bysubstituting a polyoxyethylene diol having an average molecular weightwhich is higher than 900, for instance a polyoxyethylene diol having anaverage molecular weight of 3,500 or 6,000, for all or a portion of thepolyoxyethylene dio1 which has an average molecular weight of 900. Thetarnish remover of this example is particularly effective on silver.

Example 2 4,0 This formula is also recommended for a silver polish andthe stifi product which is formed may be made thicker or more fluid inthe manner described in'Example 1.

Example 3 Thirty-seven parts of the polyoxyethylene diol of Example 1, 3parts of the wetting agent of Example 1, and 18 parts of water are mixedas described in Example 1. With these ingredients there may then beincorporated 12 parts of triethanolamine acid oxalate. When thetriethaethylene diol having an average molecular weight of about 900 anda melting point from about C. to C. and 3 parts of a wetting agent ofthe class described (allparts by weight) were stirred together until thepolyoxyethylene diol dissolved. Heat may be applied to facilitate thesolution of the polyoxyethylene diol but is not necessary. The wettingagent in this case was a 25% aqueous solution of sodium heptadecylsulfate (sodium nolamine acid oxalate has been incorporated in themixture, 30 parts of diatomaceous earth may be incorporated. Thetriethanolamine acid oxalate may be made by mixing one mol of oxalicacid with one mol of triethanolamine, the heat of the reaction beingsu'fllcient to initiate and complete the reaction. The triethanolamineacid oxalate increases the speed of action of the tarnish remover inremoving tarnish, especially on copper and brass but the composition isnot so hard on the hands as if straight oxalic acid were used. As thetriethanolamine acid oxalate is still an acidic salt, the abrasive, inthis case, may be silica but preferably is the softer diatomaceous earthinstead of chalk which might react with the acid oxalate. The wettingagent not only facilitatesthe action of the composition in removingtarnish from the metal but enables the composition to be removed veryeasily from the cleaned and polished metal merely by flushing the metalwith water and thus is a particularly desirable ingredient for tarnishremovers, for instance those for use on silver, or copper, or brass,which are intended for use in the home. The

consistency of the product formed in the manner stated above, may bechanged in the manner stated in Example 1.

Example 4 A composition of cream-like viscosity may be made with 2 partsof the polyoxyethylene diol of Example 1, 1 part of water and suflicientwhite rouge to give the consistency desired. Such a product has beenfound to be very effective in removing from steel tool dies the tarnishoccasioned by reason of the dies having been subjected to fire when thebuilding in which they were located was burned. Usually, polishes for ahard metal such as steel require the presence of a hard, sharp cuttingabrasive such as emery or silica.

Example 5 Thirty-seven parts of a normally solid polyoxyethylene diolhaving an average molecular weight of approximately 3500 and a meltingpoint from about 54 C. to 57 C., 3 parts of the wetting agent of Example1, and 21 parts of water are stirred together until the diol isdissolved. If desired, the mix may be heated to facilitate solution ofthe diol or the diol may be melted prior to stirring'in the wettingagent and the water. Into the fluid mass, either hot or cold, arethoroughly mixed 39 parts of chalk. At room temperature the compositionhas the consistency Of. Detrolatum and will hold its own shape. It is anefficient tarnish remover for use on brass and silver.

Example 6 Thirty-eight parts of the normally solid polyoxyethylene diolof Example 1, 3 parts of a fatty Example 7 Thirty-seven parts of thepolyoxyethylene diol of Example 1, 5 parts of a sulfated aromatic etheralcohol wetting agent, 16 parts of water, 12 parts of triethanolamineacid oxalate and 30 parts of abrasive silica are mixed in the mannerstated in the previous examples. The composition of this example has theconsistency of petrolatum and is an efllcient tarnish remover for use onbrass and copper.

Example 8 Example 9 Thirty-five parts of the polyoxyethylene diol ofExample 1, 3 parts of a 25% aqueous solution of sodium tetradecylsulfate (the sodium sulfate derivative of 3,9-dlethyltridecanol-6), 5parts of citric acid, 5 parts of sodium chloride, 25 parts of water and27 parts of diatomaceous earth are mixed in the manner stated inprevious examples. The composition of this example has the consistencyof petrolatum and is an eiiicient tarnish remover for use on aluminum,brass and copper.

In case it be desired to market a more concentrated composition intendedto be used only with an applicator wet with water, the composition ofthe following example may be prepared. Under normal circumstances theamount of water on an applicator will not reduce the proportion of thepolyoxyethylene diol lower than the 15% minimum which is necessary toprovide an emcient tarnish remover.

Example 10 Forty parts of a polyoxyethylene diol having an averagemolecular weight of about 400, and 3 parts of the wetting agent ofExample 6 are mixed. A polyoxyethylene diol of this molecular Weight isnormally a liquid. Into the mass is then incorporated suiiicient rougeto make a paste or the liquid may be added to the abrasive if sodesired. When applied by means of a wet applicator, the composition is agood tarnish remover for general household use on silver and brass asthe rouge is a relatively soft abrasive,

Example 11 A paste adapted to be used with a wet applicator may also bemade by following the procedure of Example 10 in mixing 40 parts of thepolyoxyethylene diol of Example 10, 3 parts of the wetting agent ofExample 9, 9 parts of triethanolamine acid oxalate and incorporatingsuflicient abrasive silica to make a paste. This composition contains aslight amount of water and is a good tarnish remover for generalhousehold use although the silica will cut the metal to a greater extentthan will rouge of a similar particle size.

Example 12 A tarnish remover without abrasive but containing achemically active addend and adapted to be used with a wet applicatormay be prepared by mixing 75 parts of the polyoxyethylene diol ofExample 1 with 25 parts of triethanolamine acid oxalate. Thiscomposition has a consistency similar to that of soft petroiatum and isuseful for removing tarnishing from brass and copper.

Example 13 A tarnish remover without abrasive but containing water andchemically active addends may be prepared by mixing 50 parts of thepolyoxyethylene diol of Example 1, 7 parts of citric acid, 7 parts ofsodium chloride and 36 parts of water. This composition is a slightlyviscous liquid and is useful for removing tarnish from brass, copper andaluminum.

In general, the tarnish removing compositions should contain from 15 to60 parts of the polyoxyethylene diol, a polyoxyethylene diol having a.melting point between about 30 C. and 40 C. being preferred as itappears to be the most active and, being normally a solid, allows theincorporation of water in the composition without requiring too muchfiller or abrasive to keep the composition in the cream-like condition;from 10 to 50 parts of abrasive; from a small quantity to 30 parts ofwater; and addends up to 20 parts; the weight of the polyoxyethylenediol being not less than 15 parts by weight of the total composition.

It is to be understood that the compositions may contain suitableperfumes, colors and fillers as desired provided their incorporationdoes not decrease the proportion of polyoxyethylene diol below the 15%minimum and preferably does not decrease the abrasive below the 10%minimum. However, the use of adulterants is not recommended. If fillersor extenders are used, they should be discrete particulate non-filmingmaterials. for instance wood flour and not materials which leavewater-insoluble fllms on the metal,

for instance water-insoluble oils and waxes. The compositions should betree from water-inaok uble film forming materials or materials whichform water-insoluble films or scum.

From the previous description it will be seen that, by the use of thepclyoxyethylene diols, I am enabled to provide an emcient metal cleaner,Polish and tarnish remover, including either hard or soft water; onewhich is substantially nonrlammable and non-poisonous; one which is notgreasy; one which does not form a waterinsoluble scum or fllm on themetal to be cleaned: one which does not foam; one which may easily beremoved from the cleansed metal merely by flushing with water; one whichmay contain a minimum of addend and one'which has a minimum ofdeleterious eflect on the person using the product, thereby renderingunnecessary special protective devices, such as waterproof gloves andthe like.

What is claimed is:

1. A composition for removing tarnish from metals comprising water,abrasive particles, a polyoxyethylene diol having an average molecularweight of not less than about 400, a tarnishremoving substancechemically active in attacking the tarnish and acting to chemicallyremove the tarnish in conjunction with said diol, and a metal-wettingagent eflective in causing the composition to wet the tarnish, said diolbeing not substantially less than about percent by weight of thecomposition.

2. A tarnish-remover base composition adapted to be mixed with water toform a composition for removing tarnish from metals, said basecomposition comprising abrasive particles, a polyoxyethylene diol havingan average molecular weight of not less than about 9100, atarnish-removing substance chemically active in attacking the tarnishand acting in. said tarnish-removing composition to chemically removethe tarnish in con- Junction with said diol, and a metal-wetting agenteffective in causing said tarnish-removing composition to wet thetarnish, said diol being not substantially less than about 15 percentbyweight of the base composition.

3. A tarnish-remover base composition adapted to be mixed with water toform a composition for removing tarnish from metals. said basecornposition comprising abrasive particles, a polyoxyethylene diolhaving an average molecular weight oi'not less than about 400, and atarnish, removing substance chemically active in attacking the tarnishand acting in said tarnish-removing composition to chemically remove thetarnish in conjunction withsaid diol, said diol being not substantiallyless than about 15 ,percent by weight'ci the base composition.

4. A tarnish-remover base composition adapted to be mixed with water toform a composition ior removing tarnish from metals, said basecomposition comprising abrasive particles, a poly oxyethylene diolhaving an average molecular weight of not less than about 400, and ametalwetting agent effective in causing said tarnishremoving compositionto wet the tarnish, said diol being not substantially less than about 15percent by weight of the base composition.

5. A fluid tarnish-remover base composition adapted to be mixed withwater to form a composition tor removing tarnish from metals, said basecomposition comprising a polyoxyethylene diol having an averagemolecular weight of not less than about 400, and an acidic ammonium saltchemically active in attacking the tarnish and acting in saidtarnish-removing composition to chemically remove the tarnish inconjunction with said diol, said diol being not substantially less thanabout 15 percent by weight of the base composition.

6. A fluid tarnish-remover base composition adapted to be mixed withwater to form a composition for removing tarnish from metals, said basecomposition comprising a poly-oxyethylene diol having an averagemolecular weight of not less than about 400, and an acidictarnish-removing substance comprising an acid and a salt and chemicallyafctive in attacking the tarnish and acting in saidtarnish-removingcomposition to chemically remove the tarnish in conjunction with saiddiol, said diol being not substantially less than about 15 percent byweight of the base composition.

7. A fluid tarnish-remover base composition adapted to be mixed withwater to form a composition for removing tarnish from metals, said basecomposition comprising a polyoxyethylene diol having an averagemolecular weight 0! not less than about 400, and a tarnish-removingsubstance comprising an amine acid salt and chemically active inattacking the tarnish and acting in said tarnish-removing composition tochemically remove the tarnish in conjunction with said 'diol, said diolbeing not substantially less than about 15 percent by weight of the basecomposition.

8. A fluid tarnish-remover base composition adapted to be mixed withwater to form a composition for removing tarnish from metals, said basecomposition comprising a polyoxyethylene diol having an averagemolecular weight of not less than about 400, and a tarnish-removingsubstance comprising an alkylol amine acid salt and chemically active inattacking the tarnish and acting in said tarnish-removing composition tochemically remove the tarnish in conjunction with said diol, said diolbeing not substantially less than about 15 percent by weight of the basecomposition.

9. A fluid tarnish-remover base composition adapted to be mixed withwater to form a composition for removing tarnish from metals, said basecomposition comprising a polyoxyethylene diol having an averagemolecular weight of not less than about 400. and a tarnish-removingsubstance comprising an ammonium compound and chemically active inattacking the tarnish and acting in said tarnish-removing composition tochemically remove the tarnish in conjunction with said diol, said diolbeing not substantially less than about 15 percent by weight of the basecomposition.

10. A tarnish-remover base composition adapted to be mixed with water toform a composition for removing tarnish from metals, said basecomposition comprising a polyoxyethylene diol having an averagemolecular weight of not less than about 400, abrasive particles, and anacidic tarnish-removing substance comprising an organic acid and a saltand chemically active in attacking the tarnish and acting in saidtarnish removing composition to chemically remove the tarnish inconjunction with said diol, said diol being not substantially less thanabout 15 percent by weight of the base composition.

11. A composition for removing tarnish from metals comprising apoiyoxyethylene diol having an average molecular weight of not less thanabout 400, a solvent for said diol, an acidic tarnish-removing substancechemically active in attacking the tarnish and acting to chemicallyremove the tarnish in conjunction with said diol, a metal-wetting agent,and a tarnish-cutting abrasive non-reactive with the other ingredientsof the composition, the amount of said diol being not substantially lessthan about 15 percent by weight of the composition.

12. A composition for removing tarnish from metals comprisingapproximately 37 parts of a polyoxyethylene diol having a melting pointbetween about 30 C. and 40 0., approximately 12 parts of a water-solubletarnish-removing substance chemically active in attacking the tarnishand acting to chemically remove the tarnish in conjunction with saiddiol, approximately parts of an abrasive, approximately 1 part of sodiumheptadecyl sulfate and sufficient water to make 100 parts, all parts byweight.

'13. A composition for removing tarnish from metals comprising betweenabout 15 parts and 60 parts of a polyoxyethylene diol having a meltingpoint between about 30 C. and 40 C-, from a small quantity up to about20 parts 01' triethanol amine acid oxalate, from about 10 parts to aboutparts of diatomaceous earth, approximately 1 part of sodium heptadecylsulfate, and from a small quantity up to about 30 parts of water, allparts by weight, the amount of said diol being not substantially lessthan 15 percent by weight of the composition.

HELEN E. WASSELL.

